The present invention relates generally to an alkyl allyl amine, more particularly to a polymer formed from an alkyl allyl amine, and even more particularly the present invention relates to a hair fixative composition utilized in styling gels, mousses or sprays (aerosol or pump) which includes a polymerizate of an alkyl allyl amine. It is preferable that the aqueous hair styling composition of the present invention contain a low concentration of volatile organic compounds (VOCs), with it being preferable that the VOCs make up 80% or less of the overall concentration of the hair spray formulation, and even more preferably that the VOCs make up 55% or less of the overall concentration of the hair spray formulation.
Hair fixing or styling formulations are used to hold hair in a particular shape or configuration. They can take the form of, for example, hair sprays (aerosol or pump), styling gels, spray-on gels, or mousses. Hair styling formulations normally form a thin film of hair fixative resin when applied to the hair. This thin film of resin holds adjacent hairs together to retain a particular shape or configuration. When the hair styling composition is formulated as a spray it is most common to use a propellant (i.e. an aerosol) in the hair styling formulation. This normally adds to the overall VOC content of the hair spray formulation.
Hair fixing or styling formulations typically contain one or more volatile organic compound (VOC). VOCs as defined by the Environmental Protection Agency (EPA) contain at least one carbon atom and are typically used as solvents or propellants in the hair styling compositions. VOCs contribute to ground level air pollution in the presence of sunlight and air, and are volatile under ambient conditions. VOCs include, for example, C1 to C12 straight or branched chain alcohols such as methanol, ethanol, propanol, isopropanol, or butanol; C1 to C12 straight or branched chain hydrocarbons such as methane, ethane, propane, isopropane, isobutane, pentane, isopentane, or butane; or ethers such as dimethyl ether, or dimethoxymethane.
Aerosol hair sprays traditionally were formulated to contain 90-95% VOC in the form of ethanol and hydrocarbon propellants. In April 1996, the EPA published the first nationwide VOC regulations for consumer and commercial products, requiring all hair spray to meet an 80% VOC limit by March 1997. Air pollution issues in heavily populated metropolitan areas such as California are required to have more stringent regulations than the EPA, making these areas the bellwether for mass VOC regulations. The California Air Resources Board has had an 80% VOC limit in effect since 1993 and currently plans to enforce a 55% VOC limit on hair sprays by mid-year 1999. Other states with highly populated areas, such as New York, Connecticut and Texas, have also considered enacting a 55% VOC limit.
The 55% VOC limit is much more of a challenge from a technical perspective than the 80% limit because the addition of large amounts of water to the hair spray formulation negatively affects both the hold performance and spray characteristics of the hair spray. Water impacts hold performance because it contributes to an increase in solution viscosity and surface tension. This results in increased initial curl droop and extends both tack time and dry time. Spray performance is impacted because an increase in viscosity (generally greater than 15 centipoise) of the spray solution leads to coarser, wetter sprays which are inefficient in coating the hair. In addition, the introduction of water causes compatibility problems in the ethanol/hydrocarbon solvent/propellant systems used for hair sprays, and can also lead to corrosion problems in steel cans used as vessels for the hair sprays.
Water can also cause the composition, when sprayed, to form droplets or beads on the hair. These beads leave undesirable visible residue on the hair when dried, and can impart a raspy feel to the hair when combed. Water soluble hair fixative resins, when used in low VOC hair styling formulations, are also more likely to become tacky after being applied to the hair. The water soluble hair fixative resins in a low VOC hair styling formulations may also have poor curl retention properties due to their inability to dry completely when applied to the hair.
These undesirable properties become particularly severe when the hair styling formulation contains 15 weight percent or more water. As a result, hair styling formulators have begun to redesign their hair styling compositions in order to formulate hair styling compositions or hair sprays which achieve low VOC levels, but yet which are acceptable for their intended use. In this regard, hair style formulators have focussed on using solvents which are not classified as VOCs and on developing resins which are suitable in low VOC formulations. A resin is considered suitable when it can be applied to the hair in a carrier at low VOC and form a smooth feeling film and is resistant to cracking or breaking when combed. An example of a low VOC hair styling formulation already developed is U.S. Pat. No. 5,176,898 to Goldberg, et al., which discloses an aqueous hair spray formulation having less than 80 weight percent VOC. The aqueous hair spray formulation contains from 1 to 10 weight percent volatile silicone, preferably cyclomethicone or dimethicone copolyol, from 15 to 40 weight percent water/alcohol solution, from 5 to 60 weight percent propellant, from 1 to 10 weight percent water soluble hair fixative resin, and from 0.05 to 3.0 weight percent neutralizer/plasticizer.
The present invention is directed to an alkyl allyl monomer and polymers thereof, particularly an alkyl allyl monomers useful in a hairspray formulation. More particularly the present invention is directed to a hair spray formulation which satisfies low VOC standards now in place and those anticipated in the future, and which overcomes a number of undesirable characteristics found in known low VOC hair spray formulations (i.e., decreased hold, increased tackiness, larger particle size, poor spray patterns, increased drying times, instability due to hydrolysis, increased can corrosion and poor compatibility with the solvent.
The present invention is directed to an alkyl allyl amine represented by the formula: 
wherein R1 represents hydrogen or an allyl, R2 represents hydrogen or methyl, n is an integer from 0 to 6, R4, R5 and R6 each independently represent a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having 3 to 22 carbon atoms, a cycloalkylene (i.e. an aryl group) having 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
It is preferable that at least one of R4, R5 or R6 represent a substituent other than hydrogen, and more preferable that the alkyl portion of the alkyl allyl amine represented in formula (2) below be a branched alkyl group, more preferably, a tertiary alkyl group, more preferably a tertiary butyl group, and most preferably a tertiary octyl group: 
The alkyl group may also include methylene spacers (nxe2x89xa71) before the alkyl group begins to branch. The alkyl group may also include a hetero atom or a functional group. It is preferable that the alkyl allyl amine be a tertiary octyl mono allyl amine represented by formula (3) below: 
wherein R2 represents hydrogen or methyl.
There appears to be a beneficial effect when the alkyl allyl amines of the present invention are symmetrical. It is speculated that the benefit is due to a more rigid polymer structure. Thus, it is more preferable that R1 of Formula (1) represent an allyl group, with R2 and R3 each independently representing a hydrogen or methyl group, with it being most preferred that R2 and R3 be the same, and even more preferred that both R2 and R3 both be hydrogen. Formula (4) below illustrates a preferred alkyl diallyl amine which has a substantial degree of xe2x80x9csymmetryxe2x80x9d: 
wherein R2 and R3 each independently represent hydrogen or methyl, n is an integer from 0 to 6, R4, R5 and R6 each independently represent a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having from 3 to 22 carbon atoms, a cycloalkylene (i.e. an aryl group) having from 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
As with the alkyl mono allyl amine, it is also preferred that the alkyl portion of the diallyl amine be a branched alkyl group, more preferably a tertiary group (see Formula (2)) such as a tertiary butyl group, and even more preferred that it be a tertiary octyl group. Such a preferred embodiment, for instance, t-octyl diallyl amine (TODA), may be represented by the formula: 
The present invention also relates to a hair fixative resin comprised of a polymer formed from an alkyl allyl amine monomer. The alkyl allyl amine monomer may be either a alkyl diallyl amine (i.e. formula (4)) or an alkyl mono allyl amine (i.e. formula (1) wherein R1 is hydrogen). The polymer may be generally represented by the formula:
xe2x80x83[L]xxe2x80x94[M]yxe2x80x94[N]zxe2x80x83xe2x80x83(6)
where x, y and z are integers equal to or greater than 1 and a sum of x, y and z is an integer greater than 5, and where L, M and N represent a conversion unit of a monomer which may be the same or different from each other. L, M, and Z may be random or repeating sequences of a conversion unit of a monomer with at least one of L, M and N being a conversion unit of an alkyl mono allyl amine (i.e. the polymerizate of formula (1) wherein R1 is H) or a conversion unit of alkyl diallyl amine of formula (7) shown below: 
wherein
R2 and R3 each independently represent hydrogen or methyl,
l is 0 or 1, if l is 0, m is 1, and if l is 1, m is 0,
n is 0 to 6, and
R4, R5 and R6 each independently represent hydrogen, an alkyl group having from 1 to 22 carbon atoms, a cycloalkyl group having from 3 to 22 carbon atoms, a cycloalkene (i.e. an aryl group) having from 6 to 22 carbon atoms or an alkylaryl group having from 7 to 22 carbon atoms.
It is preferable that the polymer be formed as a homopolymer, that is, where L, M and N are all the conversion product of either the alkyl allyl amine monomer of formula (3), the conversion product of the alkyl diallyl amine of formula (5) (i.e. that of formula (7)), or a conversion unit of another known monomer. In the where L, M and N are different, the conversion units appear in a regular sequence. Even more preferably the polymer is a copolymer formed from, for example a monomer of Formula (5) and Formula (3), a methyl methacrylate monomer, or acrylic acid monomer or a combination thereof, For example, L, M and N of formula (6) may be a conversion unit of any (meth)acrylate or (meth)acrylic acid (i.e., methyl methacrylate, acrylic acid) as well as an alkyl diallyl amine or alkyl mono allyl amine in a regular or random sequence. Other monomers which may be used in conjunction with either the alkyl diallyl amine and/or alkyl mono allyl amine of the present invention include a monomer selected from the group consisting of (meth)acrylates, acrylamides, and (di)allyl ammonium salts. For example, acrylamide, butyl aminoethyl methacrylate, methyl octyl diallyl ammonium bromide, dimethylamino ethylacrylate, tertiary-octyl acrylamide, and isobornyl methacrylate are suitable monomers useful in the present invention.
It is preferable that the polymer of formula (6) include a conversion unit of the alkyl diallyl amine and that the that the alkyl group of the alkyl allyl amine be a branched alkyl group, more preferably a tertiary butyl group, and most preferably a tertiary octyl group. The polymer formed from a tertiary octyl diallyl amine monomer may be represented by formula (8) below: 
wherein each of R2, R3, R4, R5, R6, l, m, n, L, N, x, y and z have the same definition as with regard to formula (6) and (7) above and wherein at least one of R4, R5 and R6 of formula (8) are an alkyl group, even more preferably a t-alkyl group represented by Formula (2) above.
In the most preferred embodiment of the present invention, the polymer is incorporated in a hair spray or fixative formulation comprised of a volatile organic compound at a weight percentage of less than 80%, more preferably a hair spray formulation having a VOC concentration less than 55%. Typically, the hair spray formulation includes water and/pr other exempt solvents. The hair spray formulation preferably includes a VOC selected from the group consisting of methanol, an alcohol (i.e., ethanol, propanol, isopropanol, butanol) dimethoxymethane, and dimethyl ether. The hair spray formulation may also include acetone, typically classified as a solvent exempt from the VOC category as well as other solvents exempt from the VOC classification. It is preferable that the hair fixative formulation be formed at least in part with the monomer of formula (1), more preferably from a monomer wherein R1 of formula (1) is an allyl group and the alkyl portion of formula (1) is tertiary alkyl, more preferably t-octyl as shown in formula (4) above.
The present invention is also directed to a method of manufacturing a hair fixative comprised of polymerizing an alkyl allyl monomer either as a homopolymer or a copolymer preferably along with methyl methacrylate and/or acrylic acid monomer. It is preferable that water and carrier solvents, including VOC solvents are mixed with the polymer and that, the overall concentration of VOCs in the hair spray formulation are less than 80% (wt/wt %) and more preferably less than 55% (wt/wt %) or less VOC.
The features, aspects and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where: